Process to produce biofuels via organic phase thermal hydrocatalytic treatment of biomass

ABSTRACT

Biofuels can be produced via an organic phase hydrocatalytic treatment of biomass using an organic solvent that is partially miscible with water. An organic hydrocarbon-rich phase from the hydrocatalytically treated products can be recycled to form at least a portion of the organic phase.

The present application claims the benefit of U.S. Patent ApplicationNo. 61/553,582, filed Oct. 31, 2011, the entire disclosure of which ishereby incorporated by reference.

FIELD OF THE INVENTION

The invention relates to the production of higher hydrocarbons suitablefor use in transportation fuels and industrial chemicals from biomass.

BACKGROUND OF THE INVENTION

A significant amount of attention has been placed on developing newtechnologies for providing energy from resources other than fossilfuels. Biomass is a resource that shows promise as a fossil fuelalternative. As opposed to fossil fuel, biomass is also renewable.

Biomass may be useful as a source of renewable fuels. One type ofbiomass is plant biomass. Plant biomass is the most abundant source ofcarbohydrate in the world due to the lignocellulosic materials composingthe cell walls in higher plants. Plant cell walls are divided into twosections, primary cell walls and secondary cell walls. The primary cellwall provides structure for expanding cells and is composed of threemajor polysaccharides (cellulose, pectin, and hemicellulose) and onegroup of glycoproteins. The secondary cell wall, which is produced afterthe cell has finished growing, also contains polysaccharides and isstrengthened through polymeric lignin covalently cross-linked tohemicellulose. Hemicellulose and pectin are typically found inabundance, but cellulose is the predominant polysaccharide and the mostabundant source of carbohydrates. However, production of fuel fromcellulose poses a difficult technical problem. Some of the factors forthis difficulty are the physical density of lignocelluloses (like wood)that can make penetration of the biomass structure of lignocelluloseswith chemicals difficult and the chemical complexity of lignocellulosesthat lead to difficulty in breaking down the long chain polymericstructure of cellulose into carbohydrates that can be used to producefuel.

Most transportation vehicles require high power density provided byinternal combustion and/or propulsion engines. These engines requireclean burning fuels which are generally in liquid form or, to a lesserextent, compressed gases. Liquid fuels are more portable due to theirhigh energy density and their ability to be pumped, which makes handlingeasier.

Currently, bio-based feedstocks such as biomass provide the onlyrenewable alternative for liquid transportation fuel. Unfortunately, theprogress in developing new technologies for producing liquid biofuelshas been slow in developing, especially for liquid fuel products thatfit within the current infrastructure. Although a variety of fuels canbe produced from biomass resources, such as ethanol, methanol, andvegetable oil, and gaseous fuels, such as hydrogen and methane, thesefuels require either new distribution technologies and/or combustiontechnologies appropriate for their characteristics. The production ofsome of these fuels also tends to be expensive and raise questions withrespect to their net carbon savings. There is a need to directly processbiomass into liquid fuels.

SUMMARY OF THE INVENTION

In an embodiment, a method comprises:

-   -   (a) providing a biomass feedstock containing cellulose and        water;    -   (b) contacting the biomass feedstock with an organic solvent        having partial miscibility with water at 25° C. to form a        digested biomass stream containing the organic solvent and        water, at an organic solvent to water mass ratio of greater than        1:1;    -   (c) contacting the digested biomass stream with molecular        hydrogen in the presence of a metal catalyst capable of        activating molecular hydrogen, under organic phase hydrothermal        conditions to form a hydrocatalytically treated mixture that        contains a plurality of hydrocarbon molecules and oxygenated        hydrocarbon molecules,    -   (d) phase separating the hydrocatalytically treated mixture, by        liquid-liquid separation, into an organic hydrocarbon-rich phase        and a water phase comprising water soluble oxygenated        hydrocarbons;    -   (e) providing at least a portion of the organic hydrocarbon-rich        phase to step (b) to form at least a portion of the organic        solvent; and    -   (f) processing at least a portion of the water phase, at least a        portion of the organic hydrocarbon-rich phase, or at least a        portion of both water phase and organic hydrocarbon-rich phase,        to form a fuel blend comprising higher hydrocarbons.

The features and advantages of the invention will be apparent to thoseskilled in the art. While numerous changes may be made by those skilledin the art, such changes are within the spirit of the invention.

BRIEF DESCRIPTION OF THE DRAWING

This drawing illustrates certain aspects of some of the embodiments ofthe invention, and should not be used to limit or define the invention.

The FIGURE schematically illustrates a block flow diagram of anembodiment of a higher hydrocarbon production process 100 of thisinvention.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to the production of higher hydrocarbons suitablefor use in transportation fuels and industrial chemicals from biomass.The higher hydrocarbons produced are useful in forming transportationfuels, such as synthetic gasoline, diesel fuel, and jet fuel, as well asindustrial chemicals. As used herein, the term “higher hydrocarbons”refers to hydrocarbons having an oxygen to carbon ratio less than theoxygen to carbon ratio of at least one component of the biomassfeedstock. As used herein the term “hydrocarbon” refers to an organiccompound comprising primarily hydrogen and carbon atoms, which is alsoan unsubstituted hydrocarbon. In certain embodiments, the hydrocarbonsof the invention also comprise heteroatoms (i.e., oxygen sulfur,phosphorus, or nitrogen) and thus the term “hydrocarbon” may alsoinclude substituted hydrocarbons. The term “soluble carbohydrates”refers to oligosaccharides and monosaccharides that are soluble in thedigestive solvent and that can be used as feedstock to thehydrogenolysis reaction (e.g., pentoses and hexoses). “

Aqueous phase” refers to a liquid phase that can be diluted by water at1:1 or greater water/liquid-phase ratio, without separating into asecond liquid phase. The second liquid phase is defined as a phasehaving an interfacial tension greater than zero relative to the firstphase. Second phase formation can be identified via formation of aliquid-liquid interface which reflects and refracts light, sound, orother waves, for two phases which may separate via density difference,or remain mixed as an emulsion. If a second liquid phase forms uponaddition of water at greater than about 5 weight percent relative to thetotal mixture, the phase having the highest water concentration isdesignated as the “aqueous phase”, with the other phase called the“organic phase”. For “hydrocatalytic treatment” or “organic phasehydrocatalytic” processing, the reaction is conducted with an organicsolvent which if mixed with water at greater than 1:1 mass ratio, wouldseparate into an organic hydrocarbon-rich phase and an aqueous phase.The organic phase must solubilize some water to effect hydrolysis and“reforming” reactions. A lower limit of about 1 wt % solubility of waterin the organic solvent phase at reaction temperatures defines a solventphase suitable for “hydrocatalytic treatment.”

The methods of the invention have an advantage using the organic-richlayer from thermocatalytic processing of biomass feedstocks recycled assolvent to digest biomass. The solvent is effective in preventing tar orheavy ends deposition during biomass digestion, and in assisting withthe digestion via solvation, and recycle of carboxylic acid components.It can be used for thermocatalytic biofuels processes where thecomposition of intermediate products formed via reforming,hydrogenolysis, or hydrodeoxygenation reaction (collectivelyhydrocatalytically treated) favors the formation of a significantfraction of organic phase components, as opposed to aqueous solublecomponents. Alternately, an externally formed organic hydrocarbon-richsolvent may be deliberately added to the reaction mixture. Use of anorganic hydrocarbon-rich solvent improves the solubilization of hydrogeninto the reaction mixture relative to that which can be obtained with anaqueous phase solvent. It also allows for convenient recycle of theorganic solvent phase via liquid-liquid separation and decant, followingbiomass digestion and reaction. Because biomass is most economically fedto a biofuels process as a wetted or only partially dried feedstock, andbecause water is formed upon catalytic addition of hydrogen to biomassand biomass-derived intermediates, physical separation of excess waterand organic hydrocarbon-rich solvent after the digestion and reactionstep, is a process advantage in requiring less energy and equipment,relative to the use of thermal distillation to separate solvents fromwater in a aqueous solvent-based process.

The process is therefore more energy efficient and more effective inhydrocatalytic processing, including hydrogenation, hydrodeoxygenationand hydrogenolysis of biomass-derived intermediates, than a comparableprocess conducted in the presence of a fully water miscible, aqueoussolvent mixture.

The organic-rich layer (organic phase) may be produced as intermediateproducts from hydrocatalytic treatment under organic phase hydrothermalconditions, and typically have a dielectric constant of greater thanabout 2, and are effective in assisting the digestion, hydrolysis andorganic phase hydrocatalytic conversion of biomass-derivedintermediates, via ability to solubilize water and ionic intermediates.

Suitable organic solvent mixtures will exhibit only partial miscibilitywhen contacted with water, such that a second liquid phase is formed inthe presence of water at least for some temperature between ambient (20°C.) and 300° C., and for at least a fraction of water between 0% and100%. Partial miscibility enables at least some components of thesolvent mixture to be conveniently recycled by liquid decant from aliquid-liquid or liquid-liquid-vapor contactor. The partially watermiscible, organic solvent mixture will be comprised of one or moreindividual components which have only partial solubility in water, asreferenced by C. L. Yaws, Chemical Properties Handbook, McGraw-Hill, NY(1999), Table 15-1. Some components of the mixture may be fully miscibleor soluble with water at room temperature, for example propanol,ethanol, acetone, acetic acid, acetaldehyde, ethylene glycol,tetrahydrofuran, but the mixture must also contain a sufficientconcentration of components containing only partial water miscibilitysuch as n-butanol, n-pentanol, n-hexanol, n-octanol, aldehydes orketones of C₄ or higher in carbon number, pentane, pentene and highmolecular weight alkenes and alkanes, such that a second,hydrocarbon-rich organic liquid phase is formed. Propensity forindividual components of the solvent mixture to partition between thehydrocarbon-rich organic phase and the excess water phase is describedby their octanol-water partition coefficient (Yaws op cit.). Water willexhibit some solubility in the hydrocarbon-rich organic phase, typicallyabove about 1 weight percent. Dielectric constant for thehydrocarbon-rich organic phase will be greater than about 2, but lessthan about 15, to comprise a solvent mixture of moderate polarity. Thesolvent provides for a finite solubility of carbohydrate intermediatessuch as glucose, fructose, mannose, xylose, xylitol, and sorbitol.

Water miscibility of organic hydrocarbon solvent mixtures is determinedfrom empirical observation, and modeled using two-component activitycoefficient models such as the Non Random Two Liquid (NTRL) model [RenonH., Prausnitz J. M., “Local Compositions in Thermodynamic ExcessFunctions for Liquid Mixtures”, AIChE J., 14(1), S.135-144, 1968]. Whileindividual constituents of an organic hydrocarbon-rich phase may befully miscible with water at ambient temperature, the mixture as anensemble will form a phase which is not fully miscible, but forms aliquid-liquid interface with finite interfacial tension, between theorganic hydrocarbon-rich phase, and the aqueous water-rich phase.Individual constituents will partition between the organic and aqueousphases, according to thermodynamic equilibrium. Prediction ofmiscibility may be based upon correlation of cohesive energy differencefor individual components as correlated by the Hildebrand solubilityparameter (Hildebrand, J. H. The Solubility of Non-Electrolytes; NewYork: Reinhold, 1936.], adapted to consider dispersion, polar, andhydrogen bonding components by Hanson (Hansen, Charles (2007). HansenSolubility Parameters: A user's handbook, Second Edition. Boca Raton,Fla.: CRC Press]) An essential feature of the current inventive processis that digestion of biomass and hydrocatalytic reactions are conductedin the presence of a organic hydrocarbon rich phase which is not fullymiscible with water and forms a second aqueous phase where water ispresent at 1:1 by mass ratio, at ambient temperature.

In one embodiment, biomass feedstock is contacted with an organicsolvent having partial water miscibility to form a digested biomassstream. The digested biomass stream is contacted with hydrogen in thepresence of a metal catalyst effective at activating molecular hydrogen(hydrocatalytic treatment) also referred as molecular hydrogenactivating catalyst, to form a hydrocatalytically treated mixture thatcontains a plurality of hydrocarbon and oxygenated hydrocarbonmolecules, where at least a portion of the organic solvent may berecycled from the organic phase of the intermediate product. Theintermediate product (hydrocatalytically treated mixture) is phaseseparated by liquid-liquid separation, into an organic hydrocarbon-richphase typically having a dielectric constant of greater than about 2,and a water phase comprising water soluble oxygenated hydrocarbons. Atleast a portion of the water phase containing the water solubleoxygenated hydrocarbons, and optionally at least a portion of theoxygenated hydrocarbon molecules in the organic phase, or both, areprocessed to form a fuel blend comprising higher hydrocarbons.

During digestion of biomass and hydrocatalytic reactions includingreforming of carbohydrates to make hydrogen, if not already present,hydrogenation, hydrogenolysis, and hydrodeoxygenation, and otherreactions, components such as alcohols or ketones greater than C₄ whichare not fully water miscible across all concentration ranges, can form,to produce an organic phase. For this invention, the organic phase isrecycled to a biomass digester and hydrocatalytic reactor, to effect“organic phase hydrocatalytic treatment”. The organic phase may resultdirectly from the selective formation of reaction products fromhydrocatalytic reaction steps, including hydrogenation, hydrogenolysis,and hydro-deoxygenation. Further reaction of these intermediates viacondensation and oligomerization reactions can also occur duringhydrocatalytic processing, to render additional reaction intermediateswhich have on partial miscibility with water, and which can be used toform the organic phase solvent. This phase is separated via aliquid-liquid phase separator and decanter.

If separation of an aqueous rich phase is not observed directly in thereactor outlet as a result of the reaction product selectivities,reduction in temperature after reaction can lead to formation ofseparate organic-rich and aqueous phases, via “Temperature induced phaseseparation” (TIPS). Alternately, an external solvent may be added(alkane, aromatic) that is not fully miscible with water, which can leadto a second phase forming in the liquid-liquid separator (ConcentrationInduced Phase Separation), insuring the ability to recycle anorganic-rich solvent phase. If the water concentration is not sufficientto induce formation of a second liquid phase after reaction, water maybe added to extract a portion of the water soluble components, andinduce a phase separation to enable recycle of an organichydrocarbon-rich phase.

In one preferred embodiment, the digestion of biomass and hydrocatalyticreactions are conducted in the presence of a single, organic phase, withno separate aqueous phase observed until after the reaction step. Thismay be facilitated by recycling light oxygenated solvents from theaqueous coproduct stream (ethanol, isopropanol, propanol, acetone). Useof flash distillation to recycle light (<C4) oxygenated solvents willenable the water and polyol components of digested biomass to bedissolved into the recycle organic solvent mixture, without forming asecond aqueous rich phase until cool down to induce TIPS, extractionwith excess water, or flash of the solvent mixture to remove themiscibilizing light oxygenated solvent.

In the invention, it is important to recycle an “organic phase” toeffect digestion of biomass and act as solvent for the hydrocatalyticreactions, where “organic phase” is defined as a phase where the ratioof water to organic components is less than 1:1, and where two liquidphases are formed upon equilibrating at ambient temperature, if the massratio of organic solvent components to water is greater than 1:1.Equilibration entails intimate mixing or other means of contacting toassure that thermodynamic equilibrium is obtained throughout themixture, and across any phase boundaries which may form.

The FIGURE schematically describes one embodiment of the formation andrecycle of the organic phase. The FIGURE shows optional flashdistillation of the aqueous coproduct stream to recycle a lightmiscibilizing solvent to blend with the organic phase recycle stream.Separation of an organic rich layer is achieved via cooling prior to theliquid-liquid separator (TIPS), or addition of a water-rich stream as“water extractant” (CIPS). In such embodiment, 100, biomass feedstock 1is provided to digestion system 10 that may have one or moredigester(s), whereby the biomass is contacted with an organic solventexhibiting partial miscibility with water at 25° C. thereby forming adigested biomass stream. The organic solvent may contain make-up solvent3 and recycled organic hydrocarbon-rich phase 35. Water is generallypresent in the organic phase solvent mixture, at a concentration of lessthan 50 weight percent, most typically less than 15 weight percent.Contacting of the organic solvent with the biomass feedstock indigestive system 10 results in formation of digested biomass stream 12.At least a portion of the digested biomass stream 12 is fed to a organicphase hydrocatalytic treatment system 20 whereby the digested biomass iscatalytically reacted with hydrogen (optionally external hydrogen may beadded 15) in the presence of a hydrocatalytic treatment metal catalystcapable of activating molecular hydrogen, to produce ahydrocatalytically treated mixture 22 exiting the hydrocatalytictreatment system 20, containing at least one partial water misciblemolecule such as, for example, n-butanol, n-pentanol, n-hexanol,n-octanol, aldehydes or ketones of C₄ or higher in carbon number,pentane, pentene and high molecular weight alkenes and alkanes, and thelike along with other water-miscible small molecules and oxygenatedmolecules such as ethylene glycol, and any added or formed aromatic orhydrocarbon solvents such as toluene, benzene, or alkanes. A portion ofthe hydrocatalytically treated mixture 22 may be directly recycled todigester 10, to control residence time and concentrations in digestionand reaction steps. The portion of the hydrocatalytically treatedmixture 22 that is not optionally recycled, is phase separated into anorganic phase and water phase by liquid-liquid separation 30 to form anorganic hydrocarbon-rich phase stream 32 (organic phase) and an aqueousphase stream 34. A portion (first portion) of the organic phase isrecycled 35 to the digestor(s) 10. Optionally, a second portion 33 ofthe organic phase may be further processed to a liquid fuel blend. Lightoxygenated solvents (ethanol, isopropanol, propanol, acetone) withvolatility greater than water, and present in aqueous hydrocatalyticallytreated mixture 34 are optionally flash distilled 40 and recycled asstream 44, to further increase the solvent strength of the organicrecycle stream. Aqueous bottoms stream 50 is optionally furtherprocessed to produce higher hydrocarbons, optionally together with theorganic hydrocatalytically treated mixture 33.

A fraction of the hydrocatalytically treated mixture stream 22 mayoptionally be directly recycled to digester 10 (not shown), to providesolvent for hydrolysis and dilution the digested biomass stream 12.

Any suitable (e.g., inexpensive and/or readily available) type ofbiomass can be used. Suitable lignocellulosic biomass can be, forexample, selected from, but not limited to, forestry residues,agricultural residues, herbaceous material, municipal solid wastes,waste and recycled paper, pulp and paper mill residues, and combinationsthereof. Thus, in some embodiments, the biomass can comprise, forexample, corn stover, straw, bagasse, miscanthus, sorghum residue,switch grass, bamboo, water hyacinth, hardwood, hardwood chips, hardwoodpulp, softwood, softwood chips, softwood pulp, and/or combination ofthese feedstocks. The biomass can be chosen based upon a considerationsuch as, but not limited to, cellulose and/or hemicelluloses content,lignin content, growing time/season, growing location/transportationcost, growing costs, harvesting costs and the like.

Prior to treatment with the organic solvent, the undigested biomass canbe washed and/or reduced in size (e.g., chopping, crushing or debarking)to a convenient size and certain quality that aids in moving the biomassor mixing and impregnating the chemicals from digestive solvent. Thus,in some embodiments, providing biomass can comprise harvesting alignocelluloses-containing plant such as, for example, a hardwood orsoftwood tree. The tree can be subjected to debarking, chopping to woodchips of desirable thickness, and washing to remove any residual soil,dirt and the like.

It is recognized that washing with water prior to treatment with organicsolvent is desired, to rinse and remove simple salts such as nitrate,sulfate, and phosphate salts which otherwise may be present. This washis accomplished at a temperature of less than about 60 degrees Celsius,and where hydrolysis reactions comprising digestion do not occur to asignificant extent. In the digestion system, the size-reduced biomass iscontacted with the organic solvent in at least one digester where thedigestion reaction takes place.

The digester can be, for example, a pressure vessel of carbon steel orstainless steel or similar alloy. The digestion system can be carriedout in the same vessel or in a separate vessel. The digestion can beconducted in continuous or batch mode. The organic solvent is discussedin detail above. The contents can be kept at a temperature within therange of from 100° C. to 300° C. for a period of time, more preferablywithin the range from about 140° C. to about 260° C. The period of timecan be from about 1 to 10 hours, preferably from about 2 to about 6hours, after which the pretreated contents of the digester aredischarged. Alternately, continuous contacting of solvent though adigester may be employed. For adequate penetration, a sufficient volumeof organic solvent is required to ensure that all the biomass surfacesare wetted. Sufficient organic solvent is supplied to provide thespecified solvent to bio-based feedstock ratio. The effect of greaterdilution is to decrease the concentration of active biomass-derivedintermediates in the reaction mixture, which increases the equipmentsize and process energy required to separate reaction products from bothorganic and aqueous solvent phases, prior to subsequent processingsteps. For a continuous process, the ratio of organic hydrocarbon-richsolvent flow to biomass feed flow may be increased, to reduce theresidence time of digestive intermediates in the digester, and thusreduce their degradation via undesired thermal reactions. Preferably, apressure from about 7 bar to 200 bar, and most typically from about 15bar to 150 bar, is maintained on the system to avoid boiling or flashingaway of the solvent. The amount of water present in the biomassfeedstock should be less than about 50% by weight, based on the solidbiomass so that a separate water phase does not form in the digester andreactor upon formation of the digestive mixture.

In some embodiments, the reactions described are carried out in anysystem of suitable design, including systems comprising continuous-flow,batch, semi-batch or multi-system vessels and reactors. One or morereactions or steps may take place in an individual vessel and theprocess is not limited to separate reaction vessels for each reaction ordigestion. In some embodiments the system of the invention utilizes afluidized catalytic bed system. Preferably, the invention is practicedusing a continuous-flow system at steady-state equilibrium.

Each reactor vessel of the invention preferably includes an inlet and anoutlet adapted to remove the product stream from the vessel or reactor.In some embodiments, the vessel in which at least some digestion occursmay include additional outlets to allow for the removal of portions ofthe reactant stream. In some embodiments, the vessel in which at leastsome digestion occurs may include additional inlets to allow foradditional solvents or additives.

The digestion step may occur in any contactor suitable for solid-liquidcontacting. The digestion may for example be conducted in a single ormultiple vessels, with biomass solids either fully immersed in liquidorganic solvent, or contacted with solvent in a trickle bed or piledigestion mode. As a further example, the digestion step may occur in acontinuous multizone contactor as described in U.S. Pat. No. 7,285,179(Snekkenes et al., “Continuous Digester for Cellulose Pulp includingMethod and Recirculation System for such Digester”), which disclosure ishereby incorporated by reference. Alternately, the digestion may occurin a fluidized bed or stirred contactor, with suspended solids. Thedigestion may be conducted batch wise, in the same vessel used forpre-wash, post wash, and/or subsequent reaction steps. The digestion mayalso be conducted in a counter-flow as described in the FIGURE.

Digestion of biomass occurs in the presence of water, to effecthydrolysis reactions. A minimum of about one weight percent water isrequired in the digester, to effect these reactions. Water is in mostcases present in the biomass feed, and is also solubilized at anequilibrium concentration in the organic solvent mixture recycled fromthe liquid-liquid phase separation and decant (30). Hydrolysis ofcellulose and hemicelluloses in the biomass feed results insolubilization of carbohydrate components into the digested biomassstream.

The relative composition and concentration of the various carbohydratecomponents in the digested biomass stream affects the formation ofundesirable by-products such as tars or heavy ends in the hydrogenolysisreaction. In particular, a low concentration of carbohydrates present asreducing sugars, or containing free aldehyde groups, in the digestedbiomass stream can minimize the formation of unwanted by-products. Inpreferred embodiments, it is desirable to have a concentration of nomore than 5 wt %, based upon total liquid, of readily degradablecarbohydrates or heavy end precursors in the treated biomass, whilemaintaining a total organic intermediates concentration, which caninclude the oxygenated intermediates (e.g., mono-oxygenates, diols,and/or polyols) derived from the carbohydrates, as high as possible, viause of concerted reaction or rapid recycle of the liquid between thedigestion zone, and the hydrocatalytic reaction zone converting thesolubilized carbohydrates to oxygenated intermediates.

The hydrocatalytic treatment is conducted in the presence of molecularhydrogen, with a metal catalyst that is capable of activating molecularhydrogen (“molecular hydrogen activating catalyst”) to participation inreactions such as hydrogenation, hydrogenolysis, hydrodeoxygenation,optionally hydrodesulfurization and hydrodenitrification. Thesereactions are important for conversion of unstable reactiveintermediates derived from biomass feedstocks, to a more stable form viahydrogenation reactions, and also for generation of the desiredmono-oxygenate intermediates desired for subsequent condensation andoligomerization to liquid biofuels. If molecular hydrogen or H₂ is notpresent, most catalysts which can activate H₂ can also form H₂ fromsoluble hydrocarbons and oxygenated hydrocarbons and water, viareforming reactions. Transition metal catalysts are most typicallyemployed for activation of molecular hydrogen.

For hydrocatalytic treatment, one suitable method includes contactingthe digested biomass stream containing carbohydrate or stable hydroxylintermediate with hydrogen or hydrogen mixed with a suitable gas and ametal catalyst capable of activating molecular hydrogen to effecthydrogenation, hydrogenolysis, hydrodeoxygenation, and optionallyhydrodesulfurization and hydrodenitrification reactions under conditionseffective to form a reaction product comprising less reactive, smallermolecules or polyols and other oxygenated compounds. As used herein, theterm “smaller molecules or polyols and other oxygenated compounds”includes any molecule that has a lower molecular weight, which caninclude a smaller number of carbon atoms or oxygen atoms than thestarting carbohydrate. Less reactive refers to the conversion ofaldehydic carbonyls, to alcohols. In an embodiment, the reactionproducts include smaller molecules that include polyols and alcohols.This aspect of hydrogenolysis entails breaking of carbon-carbon bonds,where hydrogen is supplied to satisfy bonding requirements for theresulting smaller molecules, as shown for the example:

RC(H)₂—C(H)₂R′+H₂→RCH₃+H₃CR′

where R and R′ are any organic moieties.

The conditions for which to carry out hydrocatalytic treatment includingthe hydrogenation and hydrogenolysis reactions will vary based on thetype of biomass starting material and the desired products (e.g.gasoline or diesel). One of ordinary skill in the art, with the benefitof this disclosure, will recognize the appropriate conditions to use tocarry out the reaction. In general, hydrogenation reactions will startas low as 60° C., with a typical range of 80-150° C., while thehydrogenolysis reaction is conducted at temperatures in the range of110° C. to 300° C., and preferably of 170° C. to 300° C., and mostpreferably of 180° C. to 290° C.

In an embodiment, the hydrogenolysis reaction is conducted under basicconditions, preferably at a pH of 8 to 13, and even more preferably at apH of 10 to 12. In another embodiment, the hydrogenolysis reaction isconducted under neutral to mildly acidic conditions. In an embodiment,the hydrogenolysis reaction is conducted at pressures in a range betweenabout 1 and 200 bar, and preferably in a range between 15 and 150 bar,and even more preferably between 35 bar and 100 bar.

The hydrogen used in the hydrogenolysis reaction of the currentinvention can include external hydrogen, recycled hydrogen, in situgenerated hydrogen, and any combination thereof.

In an embodiment, the use of a hydrogenolysis reaction may produce lesscarbon dioxide as a byproduct, and a greater amount of polyols than areaction that results in reforming of the carbohydrate reactants togenerate hydrogen. For example, reforming can be illustrated byformation of isopropanol (i.e., IPA, or 2-propanol) from sorbitol:

C₆H₁₄O₆+H₂O→4H₂+3CO₂+C₃H₈O; dHR=−40 J/g-mol  (Eq. 1)

Alternately, in the presence of hydrogen, polyols and mono-oxygenatessuch as IPA can be formed by hydrogenolysis and hydrodeoxygenationreactions, where hydrogen is consumed rather than produced:

C₆H₁₄O₆+3H₂→2H₂O+2C₃H₈O₂; dHR=+81 J/gmol  (Eq. 2)

C₆H₁₄O₆+5H₂→4H₂O+2C₃H₈O; dHR=−339 J/gmol  (Eq. 3)

As a result of the differences in the reaction conditions (e.g.,presence of hydrogen), the products of the hydrogenolysis reaction maycomprise greater than 25% by mole, or alternatively, greater than 30% bymole of polyols, which may result in a greater conversion in asubsequent processing reaction. In addition, the use of a hydrolysisreaction rather than a reaction running at reforming conditions mayresult in less than 20% by mole, or alternatively less than 30% by molecarbon dioxide production. As used herein, “oxygenated intermediates”generically refers to hydrocarbon compounds having one or more carbonatoms and between one and three oxygen atoms (referred to herein asC1+O1-3 hydrocarbons), such as polyols and smaller molecules (e.g., oneor more polyols, alcohols, ketones, or any other hydrocarbon having atleast one oxygen atom).

In an embodiment, hydrogenolysis is conducted under neutral or acidicconditions, as needed to accelerate hydrolysis reactions in addition tothe hydrogenolysis. Hydrolysis of oligomeric carbohydrates may becombined with hydrogenation to produce sugar alcohols, which can undergohydrogenolysis.

The hydrocatalytic treatment catalyst may includes a support materialthat has incorporated therein or is loaded with a metal component, whichis or can be converted to a metal compound that has activity towards thecatalytic hydrogenation, hydrogenolysis, and hydrodeoxygenation ofsoluble carbohydrates. The support material can comprise any suitableinorganic oxide material that is typically used to carry catalyticallyactive metal components. Examples of possible useful inorganic oxidematerials include alumina, silica, silica-alumina, magnesia, zirconia,boria, titania and mixtures of any two or more of such inorganic oxides.The preferred inorganic oxides for use in the formation of the supportmaterial are alumina, silica, silica-alumina and mixtures thereof. Mostpreferred, however, is alumina.

In the preparation of the hydrocatalytic treatment catalyst, the metalcomponent of the catalyst composition may be incorporated into thesupport material by any suitable method or means that provides thesupport material that is loaded with an active metal precursor, thus,the composition includes the support material and a metal component. Onemethod of incorporating the metal component into the support material,includes, for example, co-mulling the support material with the activemetal or metal precursor to yield a co-mulled mixture of the twocomponents. Or, another method includes the co-precipitation of thesupport material and metal component to form a co-precipitated mixtureof the support material and metal component. Or, in a preferred method,the support material is impregnated with the metal component using anyof the known impregnation methods such as incipient wetness toincorporate the metal component into the support material.

When using the impregnation method to incorporate the metal componentinto the support material, it is preferred for the support material tobe formed into a shaped particle comprising an inorganic oxide materialand thereafter loaded with an active metal precursor, preferably, by theimpregnation of the shaped particle with an aqueous solution of a metalsalt to give the support material containing a metal of a metal saltsolution. To form the shaped particle, the inorganic oxide material,which preferably is in powder form, is mixed with water and, if desiredor needed, a peptizing agent and/or a binder to form a mixture that canbe shaped into an agglomerate. It is desirable for the mixture to be inthe form of an extrudable paste suitable for extrusion into extrudateparticles, which may be of various shapes such as cylinders, trilobes,etc. and nominal sizes such as 1/16″, ⅛″, 3/16″, etc. The supportmaterial of the inventive composition, thus, preferably, is a shapedparticle comprising an inorganic oxide material.

The calcined shaped particle can have a surface area (determined by theBET method employing N₂, ASTM test method D 3037) that is in the rangeof from about 50 m²/g to about 450 m²/g, preferably from about 75 m²/gto about 400 m²/g, and, most preferably, from about 100 m²/g to about350 m²/g. The mean pore diameter in angstroms (Å) of the calcined shapedparticle is in the range of from about 50 to about 200, preferably, fromabout 70 to about 150, and, most preferably, from about 75 to about 125.The pore volume of the calcined shaped particle is in the range of fromabout 0.5 cc/g to about 1.1 cc/g, preferably, from about 0.6 cc/g toabout 1.0 cc/g, and, most preferably, from about 0.7 to about 0.9 cc/g.Less than ten percent (10%) of the total pore volume of the calcinedshaped particle is contained in the pores having a pore diameter greaterthan about 350 Å, preferably, less than about 7.5% of the total porevolume of the calcined shaped particle is contained in the pores havinga pore diameter greater than about 350 Å, and, most preferably, lessthan about 5%.

The references herein to the pore size distribution and pore volume ofthe calcined shaped particle are to those properties as determined bymercury intrusion porosimetry, ASTM test method D 4284. The measurementof the pore size distribution of the calcined shaped particle is by anysuitable measurement instrument using a contact angle of 140° with amercury surface tension of 474 dyne/cm at 25° C.

In one embodiment, the calcined shaped particle is impregnated in one ormore impregnation steps with a metal component using one or more aqueoussolutions containing at least one metal salt wherein the metal compoundof the metal salt solution is an active metal or active metal precursor.The metal elements are (a) molybdenum (Mo) and (b) cobalt (Co) and/ornickel (Ni). Phosphorous (P) can also be a desired metal component. ForCo and Ni, the metal salts include metal acetates, formats, citrates,oxides, hydroxides, carbonates, nitrates, sulfates, and two or morethereof. The preferred metal salts are metal nitrates, for example, suchas nitrates of nickel or cobalt, or both. For Mo, the metal saltsinclude metal oxides or sulfides. Preferred are salts containing the Moand ammonium ion, such as ammonium heptamolybdate and ammoniumdimolybdate.

The concentration of the metal compounds in the impregnation solution isselected so as to provide the desired metal content in the finalcomposition of the hydrocatalytic treatment catalyst taking intoconsideration the pore volume of the support material into which theaqueous solution is to be impregnated. Typically, the concentration ofmetal compound in the impregnation solution is in the range of from 0.01to 100 moles per liter.

Cobalt, nickel, or combination thereof can be present in the supportmaterial having a metal component incorporated therein in an amount inthe range of from about 0.5 wt. % to about 20 wt. %, preferably fromabout 1 wt. % to about 15 wt. %, and, most preferably, from about 2 wt.% to about 12 wt. %, based on metals components (b) and (c) as metaloxide form; and the Molybdenum can be present in the support materialhaving a metal component incorporated therein in an amount in the rangeof from about 2 wt. % to about 50 wt. %, preferably from about 5 wt. %to about 40 wt. %, and, most preferably, from about 12 wt. % to about 30wt. %, based on metals components (b) and (c) as metal oxide form. Theabove-referenced weight percents for the metal components are based onthe dry support material and the metal component as the element (change“element” to “metal oxide form”?) regardless of the actual form of themetal component.

The metal loaded catalyst may be sulfided prior to its loading into areactor vessel or system for its use as hydrocatalytic treatmentcatalyst or may be sulfided, in situ, in a gas phase or liquid phaseactivation procedure. In one embodiment, the liquid soluble carbohydratefeedstock can be contacted with a sulfur-containing compound, which canbe hydrogen sulfide or a compound that is decomposable into hydrogensulfide, under the contacting conditions of the invention. Examples ofsuch decomposable compounds include mercaptans, CS₂, thiophenes,dimethyl sulfide (DMS), dimethyl sulfoxide (DMSO), sodium hydrogensulfate, and dimethyl disulfide (DMDS). Also, preferably, the sulfidingis accomplished by contacting the hydrogen treated composition, undersuitable sulfurization treatment conditions, with a suitable feedsourcethat contains a concentration of a sulfur compound. The sulfur compoundof the hydrocarbon feedstock can be an organic sulfur compound,particularly, one that is derived from the biomass feedstock or othersulfur containing amino-acids such as Cysteine.

Suitable sulfurization treatment conditions are those which provide forthe conversion of the active metal components of the precursorhydrogenolysis catalyst to their sulfided form. Typically, the sulfidingtemperature at which the precursor hydrogenolysis catalyst is contactedwith the sulfur compound is in the range of from about 150° C. to about450° C., preferably, from about 175° C. to about 425° C., and, mostpreferably, from about 200° C. to about 400° C.

When using a soluble carbohydrate feedstock that is to be treated usingthe catalyst to sulfide, the sulfurization conditions can be the same asthe process conditions under which the hydrogenolysis is performed. Thesulfiding pressure generally can be in the range of from about 1 bar toabout 70 bar, preferably, from about 1.5 bar to about 55 bar, and, mostpreferably, from about 2 bar to about 35 bar. The resulting activecatalyst typically has incorporated therein sulfur content in an amountin the range of from about 0.1 wt. % to about 40 wt. %, preferably fromabout 1 wt. % to about 30 wt. %, and, most preferably, from about 3 wt.% to about 24 wt. %, based on metals components (b) and (c) as metaloxide form.

In some embodiments, the hydrocatalytic treatment catalysts can be aheterogeneous catalyst capable of catalyzing a reaction between hydrogenand carbohydrate, oxygenated intermediate, or both to remove one or moreoxygen atoms to produce alcohols and polyols to be fed to thecondensation reactor. The hydrocatalytic treatment catalyst cangenerally include Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir, Sn, andalloys or any combination thereof, either alone or with promoters suchas W, Mo, Au, Ag, Cr, Zn, Mn, B, P, Bi, and alloys or any combinationthereof. Other effective Hydrocatalytic treatment catalyst materialsinclude either supported nickel or ruthenium modified with rhenium. Insome embodiments, the Hydrocatalytic treatment catalyst also includesany one of the supports, depending on the desired functionality of thecatalyst. The Hydrocatalytic treatment catalysts may be prepared bymethods known to those of ordinary skill in the art. In some embodimentsthe Hydrocatalytic treatment catalyst includes a supported Group VIIImetal catalyst and a metal sponge material (e.g., a sponge nickelcatalyst). Raney nickel provides an example of an activated spongenickel catalyst suitable for use in this invention. In some embodiments,the hydrocatalytic treatment in the invention is performed using acatalyst comprising a nickel-rhenium catalyst or a tungsten-modifiednickel catalyst. One example of a suitable catalyst for thehydrocatalytic treatment of the invention is a carbon-supportednickel-rhenium catalyst.

In some embodiments, a suitable Raney nickel catalyst may be prepared bytreating an alloy of approximately equal amounts by weight of nickel andaluminum with an aqueous alkali solution, e.g., containing about 25weight % of sodium hydroxide. The aluminum is selectively dissolved bythe aqueous alkali solution resulting in a sponge shaped materialcomprising mostly nickel with minor amounts of aluminum. The initialalloy includes promoter metals (e.g., molybdenum or chromium) in theamount such that 1 to 2 weight % remains in the formed sponge nickelcatalyst. In another embodiment, the Hydrocatalytic treatment catalystis prepared using a solution of ruthenium(III) nitrosyInitrate,ruthenium (III) chloride in water to impregnate a suitable supportmaterial. The solution is then dried to form a solid having a watercontent of less than 1% by weight. The solid is then reduced atatmospheric pressure in a hydrogen stream at 300° C. (uncalcined) or400° C. (calcined) in a rotary ball furnace for 4 hours. After coolingand rendering the catalyst inert with nitrogen, 5% by volume of oxygenin nitrogen is passed over the catalyst for 2 hours.

In certain embodiments, the hydrocatalytic treatment catalyst mayinclude a catalyst support. The catalyst support stabilizes and supportsthe catalyst. The type of catalyst support used depends on the chosencatalyst and the reaction conditions. Suitable supports for theinvention include, but are not limited to, carbon, silica,silica-alumina, zirconia, titania, ceria, vanadia, nitride, boronnitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, zeolites,carbon nanotubes, carbon fullerene and any combination thereof.

In an embodiment of the invention, the digested biomass streamcontaining carbohydrates may be converted into an stable hydroxylintermediate comprising the corresponding alcohol derivative through ahydrogenolysis reaction in addition to an optional hydrogenationreaction in a suitable reaction vessel (such as hydrogenation reactionas described in United States patent publication no. 20110154721 andco-pending United States patent publication no. US20110215821, whichdisclosures are hereby incorporated by reference).

The hydrocatalytically treated mixture then passes from thehydrocatalytic treatment system to at least one liquid-liquid separatorto separate the organic phase and the water phase as described above.Any water phase and organic phase liquid-liquid separation technique canbe used. The phase may phase form directly in the reactor outlet as aresult of the reaction product selectivities, reduction in temperatureafter reaction via “Temperature induced phase separation” (TIPS), use ofliquid-liquid coalescers, or by adding external solvent (alkane,aromatic) that is not fully miscible with water, which can lead to asecond phase forming in the liquid-liquid separator (ConcentrationInduced Phase Separation) such as described in detail in “Liquid-LiquidExtraction Using the Composition-Induced Phase Separation Process,” Ind.Eng. Chem. Res. 1996, 35, 2360-2368.

At least a portion of the aqueous phase stream, and optionally at leasta portion of the organic phase stream, containing oxygenatedintermediates may then pass to further processing stage. In addition, anoutlet stream from the separation stage can also be used to remove someor all of the lignin from the oxygenated hydrocatalytically treatedmixture. The lignin may be passed out of the separation stage as aseparate stream, for example as output stream.

In some embodiments, the oxygenated hydrocarbon molecules andhydrocarbon molecules in the hydrocatalytically treated mixtures(intermediates), whether via organic hydrocarbon-rich phase and/oraqueous phase (can be converted into higher hydrocarbons through aprocessing reaction shown schematically as processing reaction. In anembodiment, the processing reaction may comprise a condensation reactionto produce a fuel blend. In an embodiment, the higher hydrocarbons maybe part of a fuel blend for use as a transportation fuel. In such anembodiment, condensation of the oxygenated intermediates occurs in thepresence of a catalyst capable of forming higher hydrocarbons. While notintending to be limited by theory, it is believed that the production ofhigher hydrocarbons proceeds through a stepwise addition reactionincluding the formation of carbon-carbon bond. The resulting reactionproducts include any number of compounds, as described in more detailbelow.

In some embodiments, an outlet stream containing at least a portion ofthe intermediates can pass to a processing reaction or processingreactions. Suitable processing reactions may comprise a variety ofcatalysts for condensing one or more intermediates to higherhydrocarbons, defined as hydrocarbons containing more carbons than theprecursors. The higher hydrocarbons may comprise a fuel product. Thefuel products produced by the processing reactions represent the productstream from the overall process at higher hydrocarbon stream. In anembodiment, the oxygen to carbon ratio of the higher hydrocarbonsproduced through the processing reactions is less than 0.5,alternatively less than 0.4, or preferably less than 0.3.

The intermediates can be processed to produce a fuel blend in one ormore processing reactions. In an embodiment, a condensation reaction canbe used along with other reactions to generate a fuel blend and may becatalyzed by a catalyst comprising acid or basic functional sites, orboth. In general, without being limited to any particular theory, it isbelieved that the basic condensation reactions generally consist of aseries of steps involving: (1) an optional dehydrogenation reaction; (2)an optional dehydration reaction that may be acid catalyzed; (3) analdol condensation reaction; (4) an optional ketonization reaction; (5)an optional furanic ring opening reaction; (6) hydrogenation of theresulting condensation products to form a C4± hydrocarbon; and (7) anycombination thereof. Acid catalyzed condensations may similarly entailoptional hydrogenation or dehydrogenation reactions, dehydration, andoligomerization reactions. Additional polishing reactions may also beused to conform the product to a specific fuel standard, includingreactions conducted in the presence of hydrogen and a hydrogenationcatalyst to remove functional groups from final fuel product. A catalystcomprising a basic functional site, both an acid and a basic functionalsite, and optionally comprising a metal function, may be used to effectthe condensation reaction.

In an embodiment, the aldol condensation reaction may be used to producea fuel blend meeting the requirements for a diesel fuel or jet fuel.Traditional diesel fuels are petroleum distillates rich in paraffinichydrocarbons. They have boiling ranges as broad as 187° C. to 417° C.,which are suitable for combustion in a compression ignition engine, suchas a diesel engine vehicle. The American Society of Testing andMaterials (ASTM) establishes the grade of diesel according to theboiling range, along with allowable ranges of other fuel properties,such as cetane number, cloud point, flash point, viscosity, anilinepoint, sulfur content, water content, ash content, copper stripcorrosion, and carbon residue. Thus, any fuel blend meeting ASTM D975can be defined as diesel fuel.

The present invention also provides methods to produce jet fuel. Jetfuel is clear to straw colored. The most common fuel is anunleaded/paraffin oil-based fuel classified as Aeroplane A-1, which isproduced to an internationally standardized set of specifications. Jetfuel is a mixture of a large number of different hydrocarbons, possiblyas many as a thousand or more. The range of their sizes (molecularweights or carbon numbers) is restricted by the requirements for theproduct, for example, freezing point or smoke point. Kerosene-typeAirplane fuel (including Jet A and Jet A-1) has a carbon numberdistribution between about C8 and C 16. Wide-cut or naphtha-typeAirplane fuel (including Jet B) typically has a carbon numberdistribution between about C5 and C15. A fuel blend meeting ASTM D1655can be defined as jet fuel.

In certain embodiments, both Airplanes (Jet A and Jet B) contain anumber of additives. Useful additives include, but are not limited to,antioxidants, antistatic agents, corrosion inhibitors, and fuel systemicing inhibitor (FSII) agents. Antioxidants prevent gumming and usually,are based on alkylated phenols, for example, AO-30, AO-31, or AO-37.Antistatic agents dissipate static electricity and prevent sparking.Stadis 450 with dinonylnaphthylsulfonic acid (DINNSA) as the activeingredient, is an example. Corrosion inhibitors, e.g., DCI-4A are usedfor civilian and military fuels and DCI-6A is used for military fuels.FSII agents, include, e.g., Di-EGME.

In an embodiment, the intermediates may comprise a carbonyl-containingcompound that can take part in a base catalyzed condensation reaction.In some embodiments, an optional dehydrogenation reaction may be used toincrease the amount of carbonyl-containing compounds in the oxygenatedhydrocatalytically treated mixture to be used as a feed to thecondensation reaction. In these embodiments, the intermediates and/or aportion of the biomass feedstock stream can be dehydrogenated in thepresence of a catalyst.

In an embodiment, a dehydrogenation catalyst may be preferred for anoxygenated hydrocatalytically treated mixture comprising alcohols,diols, and triols. In general, alcohols cannot participate in aldolcondensation directly. The hydroxyl group or groups present can beconverted into carbonyls (e.g., aldehydes, ketones, etc.) in order toparticipate in an aldol condensation reaction. A dehydrogenationcatalyst may be included to effect dehydrogenation of any alcohols,diols, or polyols present to form ketones and aldehydes. The dehydrationcatalyst is typically formed from the same metals as used forhydrogenation, hydrogenolysis, or aqueous phase reforming, whichcatalysts are described in more detail above. Dehydrogenation yields areenhanced by the removal or consumption of hydrogen as it forms duringthe reaction. The dehydrogenation step may be carried out as a separatereaction step before an aldol condensation reaction, or thedehydrogenation reaction may be carried out in concert with the aldolcondensation reaction. For concerted dehydrogenation and aldolcondensation, the dehydrogenation and aldol condensation functions canbe on the same catalyst. For example, a metalhydrogenation/dehydrogenation functionality may be present on catalystcomprising a basic functionality.

The dehydrogenation reaction may result in the production of acarbonyl-containing compound. Suitable carbonyl-containing compoundsinclude, but are not limited to, any compound comprising a carbonylfunctional group that can form carbanion species or can react in acondensation reaction with a carbanion species, where “carbonyl” isdefined as a carbon atom doubly-bonded to oxygen. In an embodiment, acarbonyl-containing compound can include, but is not limited to,ketones, aldehydes, furfurals, hydroxy carboxylic acids, and, carboxylicacids. The ketones may include, without limitation, hydroxyketones,cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone,butane-2,3-dione, 3-hydroxybutane-2-one, pentanone, cyclopentanone,pentane-2,3-dione, pentane-2,4-dione, hexanone, cyclohexanone,2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone,undecanone, dodecanone, methylglyoxal, butanedione, pentanedione,diketohexane, dihydroxyacetone, and isomers thereof. The aldehydes mayinclude, without limitation, hydroxyaldehydes, acetaldehyde,glyceraldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal,heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomersthereof. The carboxylic acids may include, without limitation, formicacid, acetic acid, propionic acid, butanoic acid, pentanoic acid,hexanoic acid, heptanoic acid, isomers and derivatives thereof,including hydroxylated derivatives, such as 2-hydroxybutanoic acid andlactic acid. Furfurals include, without limitation,hydroxylmethylfurfural, 5-hydroxymethyl-2(5H)-furanone,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol,1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomersthereof. In an embodiment, the dehydrogenation reaction results in theproduction of a carbonyl-containing compound that is combined with theintermediates to become a part of the intermediates fed to thecondensation reaction.

In an embodiment, an acid catalyst may be used to optionally dehydrateat least a portion of the oxygenated hydrocatalytically treated mixture.Suitable acid catalysts for use in the dehydration reaction include, butare not limited to, mineral acids (e.g., HCl, H₂SO₄), solid acids (e.g.,zeolites, ion-exchange resins) and acid salts (e.g., LaCl₃). Additionalacid catalysts may include, without limitation, zeolites, carbides,nitrides, zirconia, alumina, silica, aluminosilicates, phosphates,titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttriumoxides, scandium oxides, magnesium oxides, cerium oxides, barium oxides,calcium oxides, hydroxides, heteropolyacids, inorganic acids, acidmodified resins, base modified resins, and any combination thereof. Insome embodiments, the dehydration catalyst can also include a modifier.Suitable modifiers include La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg,Ca, Sr, Ba, and any combination thereof. The modifiers may be useful,inter alia, to carry out a concerted hydrogenation/dehydrogenationreaction with the dehydration reaction. In some embodiments, thedehydration catalyst can also include a metal. Suitable metals includeCu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr,Mo, W, Sn, Os, alloys, and any combination thereof. The dehydrationcatalyst may be self supporting, supported on an inert support or resin,or it may be dissolved in solution.

In some embodiments, the dehydration reaction occurs in the vapor phase.In other embodiments, the dehydration reaction occurs in the liquidphase. For liquid phase dehydration reactions, an aqueous solution maybe used to carry out the reaction. In an embodiment, other solvents inaddition to water, are used to form the aqueous solution. For example,water soluble organic solvents may be present. Suitable solvents caninclude, but are not limited to, hydroxymethylfurfural (HMF),dimethylsulfoxide (DMSO), 1-methyl-n-pyrollidone (NMP), and anycombination thereof. Other suitable aprotic solvents may also be usedalone or in combination with any of these solvents.

In an embodiment, the processing reactions may comprise an optionalketonization reaction. A ketonization reaction may increase the numberof ketone functional groups within at least a portion of the oxygenatedhydrocatalytically treated mixture. For example, an alcohol or otherhydroxyl functional group can be converted into a ketone in aketonization reaction. Ketonization may be carried out in the presenceof a base catalyst. Any of the base catalysts described above as thebasic component of the aldol condensation reaction can be used to effecta ketonization reaction. Suitable reaction conditions are known to oneof ordinary skill in the art and generally correspond to the reactionconditions listed above with respect to the aldol condensation reaction.The ketonization reaction may be carried out as a separate reactionstep, or it may be carried out in concert with the aldol condensationreaction. The inclusion of a basic functional site on the aldolcondensation catalyst may result in concerted ketonization and aldolcondensation reactions.

In an embodiment, the processing reactions may comprise an optionalfuranic ring opening reaction. A furanic ring opening reaction mayresult in the conversion of at least a portion of any intermediatescomprising a furanic ring into compounds that are more reactive in analdol condensation reaction. A furanic ring opening reaction may becarried out in the presence of an acidic catalyst. Any of the acidcatalysts described above as the acid component of the aldolcondensation reaction can be used to effect a furanic ring openingreaction. Suitable reaction conditions are known to one of ordinaryskill in the art and generally correspond to the reaction conditionslisted above with respect to the aldol condensation reaction. Thefuranic ring opening reaction may be carried out as a separate reactionstep, or it may be carried out in concert with the aldol condensationreaction. The inclusion of an acid functional site on the aldolcondensation catalyst may result in a concerted furanic ring openingreaction and aldol condensation reactions. Such an embodiment may beadvantageous as any furanic rings can be opened in the presence of anacid functionality and reacted in an aldol condensation reaction using abase functionality. Such a concerted reaction scheme may allow for theproduction of a greater amount of higher hydrocarbons to be formed for agiven oxygenated intermediate feed.

In an embodiment, production of a C4+ compound occurs by condensation,which may include aldol-condensation, of the intermediates in thepresence of a condensation catalyst. Aldol-condensation generallyinvolves the carbon-carbon coupling between two compounds, at least oneof which may contain a carbonyl group, to form a larger organicmolecule. For example, acetone may react with hydroxymethylfurfural toform a C9 species, which may subsequently react with anotherhydroxymethylfurfural molecule to form a C15 species. The reaction isusually carried out in the presence of a condensation catalyst. Thecondensation reaction may be carried out in the vapor or liquid phase.In an embodiment, the reaction may take place at a temperature in therange of from about 7° C. to about 377° C., depending on the reactivityof the carbonyl group.

The condensation catalyst will generally be a catalyst capable offorming longer chain compounds by linking two molecules through a newcarbon-carbon bond, such as a basic catalyst, a multi-functionalcatalyst having both acid and base functionality, or either type ofcatalyst also comprising an optional metal functionality. In anembodiment, the multi-functional catalyst will be a catalyst having botha strong acid and a strong base functionality. In an embodiment, aldolcatalysts can comprise Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si, Ba, Al, Zn,Ce, La, Y, Sc, Y, Zr, Ti, hydrotalcite, zinc-aluminate, phosphate,base-treated aluminosilicate zeolite, a basic resin, basic nitride,alloys or any combination thereof. In an embodiment, the base catalystcan also comprise an oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al,Ga, In, Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe, or any combinationthereof. In an embodiment, the condensation catalyst comprisesmixed-oxide base catalysts. Suitable mixed-oxide base catalysts cancomprise a combination of magnesium, zirconium, and oxygen, which maycomprise, without limitation: Si—Mg—O, Mg—Ti—O, Y—Mg—O, Y—Zr—O, Ti—Zr—O,Ce—Zr—O, Ce—Mg—O, Ca—Zr—O, La—Zr—O, B—Zr—O, La—Ti—O, B—Ti—O, and anycombinations thereof. Different atomic ratios of Mg/Zr or thecombinations of various other elements constituting the mixed oxidecatalyst may be used ranging from about 0.01 to about 50. In anembodiment, the condensation catalyst further includes a metal or alloyscomprising metals, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Bi, Pb, Os, alloys andcombinations thereof. Such metals may be preferred when adehydrogenation reaction is to be carried out in concert with the aldolcondensation reaction. In an embodiment, preferred Group IA materialsinclude Li, Na, K, Cs and Rb. In an embodiment, preferred Group IIAmaterials include Mg, Ca, Sr and Ba. In an embodiment, Group IIBmaterials include Zn and Cd. In an embodiment, Group IIIB materialsinclude Y and La. Basic resins include resins that exhibit basicfunctionality. The base catalyst may be self-supporting or adhered toany one of the supports further described below, including supportscontaining carbon, silica, alumina, zirconia, titania, vanadia, ceria,nitride, boron nitride, heteropolyacids, alloys and mixtures thereof.

In one embodiment, the condensation catalyst is derived from thecombination of MgO and Al2O3 to form a hydrotalcite material. Anotherpreferred material contains ZnO and Al2O3 in the form of a zincaluminate spinel. Yet another preferred material is a combination ofZnO, Al2O3, and CuO. Each of these materials may also contain anadditional metal function provided by a Group VIIIB metal, such as Pd orPt. Such metals may be preferred when a dehydrogenation reaction is tobe carried out in concert with the aldol condensation reaction. In oneembodiment, the base catalyst is a metal oxide containing Cu, Ni, Zn, V,Zr, or mixtures thereof. In another embodiment, the base catalyst is azinc aluminate metal containing Pt, Pd Cu, Ni, or mixtures thereof.

Preferred loading of the primary metal in the condensation catalyst isin the range of 0.10 wt % to 25 wt %, with weight percentages of 0.10%and 0.05% increments between, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%,5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio ofthe second metal, if any, is in the range of 0.25-to-1 to 10-to-1,including ratios there between, such as 0.50, 1.00, 2.50, 5.00, and7.50-to-1.

In some embodiments, the base catalyzed condensation reaction isperformed using a condensation catalyst with both an acid and basefunctionality. The acid-aldol condensation catalyst may comprisehydrotalcite, zinc-aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si,Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr, or any combinationthereof. In further embodiments, the acid-base catalyst may also includeone or more oxides from the group of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn,Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and combinationsthereof. In an embodiment, the acid-base catalyst includes a metalfunctionality provided by Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinationsthereof. In one embodiment, the catalyst further includes Zn, Cd orphosphate. In one embodiment, the condensation catalyst is a metal oxidecontaining Pd, Pt, Cu or Ni, and even more preferably an aluminate orzirconium metal oxide containing Mg and Cu, Pt, Pd or Ni. The acid-basecatalyst may also include a hydroxyapatite (HAP) combined with any oneor more of the above metals. The acid-base catalyst may beself-supporting or adhered to any one of the supports further describedbelow, including supports containing carbon, silica, alumina, zirconia,titania, vanadia, ceria, nitride, boron nitride, heteropolyacids, alloysand mixtures thereof.

In an embodiment, the condensation catalyst may also include zeolitesand other microporous supports that contain Group IA compounds, such asLi, NA, K, Cs and Rb. Preferably, the Group IA material is present in anamount less than that required to neutralize the acidic nature of thesupport. A metal function may also be provided by the addition of groupVIIIB metals, or Cu, Ga, In, Zn or Sn. In one embodiment, thecondensation catalyst is derived from the combination of MgO and Al2O3to form a hydrotalcite material. Another preferred material contains acombination of MgO and ZrO2, or a combination of ZnO and Al2O3. Each ofthese materials may also contain an additional metal function providedby copper or a Group VIIIB metal, such as Ni, Pd, Pt, or combinations ofthe foregoing.

If a Group IIB, VIIB, VIIB, VIIIB, IIA or IVA metal is included in thecondensation catalyst, the loading of the metal is in the range of 0.10wt % to 10 wt %, with weight percentages of 0.10% and 0.05% incrementsbetween, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00% and 7.50%,etc. If a second metal is included, the preferred atomic ratio of thesecond metal is in the range of 0.25-to-1 to 5-to-1, including ratiosthere between, such as 0.50, 1.00, 2.50 and 5.00-to-1.

The condensation catalyst may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or may require aseparate support suitable for suspending the catalyst in the reactantstream. One exemplary support is silica, especially silica having a highsurface area (greater than 100 square meters per gram), obtained bysol-gel synthesis, precipitation, or fuming. In other embodiments,particularly when the condensation catalyst is a powder, the catalystsystem may include a binder to assist in forming the catalyst into adesirable catalyst shape. Applicable forming processes includeextrusion, pelletization, oil dropping, or other known processes. Zincoxide, alumina, and a peptizing agent may also be mixed together andextruded to produce a formed material. After drying, this material iscalcined at a temperature appropriate for formation of the catalyticallyactive phase, which usually requires temperatures in excess of 452° C.Other catalyst supports as known to those of ordinary skill in the artmay also be used.

In some embodiments, a dehydration catalyst, a dehydrogenation catalyst,and the condensation catalyst can be present in the same reactor as thereaction conditions overlap to some degree. In these embodiments, adehydration reaction and/or a dehydrogenation reaction may occursubstantially simultaneously with the condensation reaction. In someembodiments, a catalyst may comprise active sites for a dehydrationreaction and/or a dehydrogenation reaction in addition to a condensationreaction. For example, a catalyst may comprise active metals for adehydration reaction and/or a dehydrogenation reaction along with acondensation reaction at separate sites on the catalyst or as alloys.Suitable active elements can comprise any of those listed above withrespect to the dehydration catalyst, dehydrogenation catalyst, and thecondensation catalyst. Alternately, a physical mixture of dehydration,dehydrogenation, and condensation catalysts could be employed. While notintending to be limited by theory, it is believed that using acondensation catalyst comprising a metal and/or an acid functionalitymay assist in pushing the equilibrium limited aldol condensationreaction towards completion. Advantageously, this can be used to effectmultiple condensation reactions with dehydration and/or dehydrogenationof intermediates, in order to form (via condensation, dehydration,and/or dehydrogenation) higher molecular weight oligomers as desired toproduce jet or diesel fuel.

The specific C4+ compounds produced in the condensation reaction willdepend on various factors, including, without limitation, the type ofintermediates in the reactant stream, condensation temperature,condensation pressure, the reactivity of the catalyst, and the flow rateof the reactant stream as it affects the space velocity, GHSV and WHSV.Preferably, the reactant stream is contacted with the condensationcatalyst at a WHSV that is appropriate to produce the desiredhydrocarbon products. The WHSV is preferably at least about 0.1 grams ofintermediates in the reactant stream per hour, more preferably the WHSVis between about 0.1 to 40.0 g/g hr, including a WHSV of about 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35 g/g hr, andincrements between.

In general, the condensation reaction should be carried out at atemperature at which the thermodynamics of the proposed reaction arefavorable. For condensed phase liquid reactions, the pressure within thereactor must be sufficient to maintain at least a portion of thereactants in the condensed liquid phase at the reactor inlet. For vaporphase reactions, the reaction should be carried out at a temperaturewhere the vapor pressure of the oxygenates is at least about 10 kPa, andthe thermodynamics of the reaction are favorable. The condensationtemperature will vary depending upon the specific intermediates used,but is generally in the range of from about 77° C. to 502° C. forreactions taking place in the vapor phase, and more preferably fromabout 127° C. to 452° C. For liquid phase reactions, the condensationtemperature may be from about 7° C. to 477° C., and the condensationpressure from about 0.1 kPa to 10,000 kPa. Preferably, the condensationtemperature is between about 17° C. and 302° C., or between about 17° C.and 252° C. for difficult substrates.

Varying the factors above, as well as others, will generally result in amodification to the specific composition and yields of the C4+compounds. For example, varying the temperature and/or pressure of thereactor system, or the particular catalyst formulations, may result inthe production of C4+ alcohols and/or ketones instead of C4+hydrocarbons. The C4+ hydrocarbon product may also contain a variety ofolefins, and alkanes of various sizes (typically branched alkanes).Depending upon the condensation catalyst used, the hydrocarbon productmay also include aromatic and cyclic hydrocarbon compounds. The C4+hydrocarbon product may also contain undesirably high levels of olefins,which may lead to coking or deposits in combustion engines, or otherundesirable hydrocarbon products. In such event, the hydrocarbonmolecules produced may be optionally hydrogenated to reduce the ketonesto alcohols and hydrocarbons, while the alcohols and unsaturatedhydrocarbon may be reduced to alkanes, thereby forming a more desirablehydrocarbon product having low levels of olefins, aromatics or alcohols.

The condensation reactions may be carried out in any reactor of suitabledesign, including continuous-flow, batch, semi-batch or multi-systemreactors, without limitation as to design, size, geometry, flow rates,etc. The reactor system may also use a fluidized catalytic bed system, aswing bed system, fixed bed system, a moving bed system, or acombination of the above. In some embodiments, bi-phasic (e.g.,liquid-liquid) and tri-phasic (e.g., liquid-liquid-solid) reactors maybe used to carry out the condensation reactions.

In a continuous flow system, the reactor system can include an optionaldehydrogenation bed adapted to produce dehydrogenated intermediates, anoptional dehydration bed adapted to produce dehydrated intermediates,and a condensation bed to produce C4+ compounds from the intermediates.The dehydrogenation bed is configured to receive the reactant stream andproduce the desired intermediates, which may have an increase in theamount of carbonyl-containing compounds. The de-hydration bed isconfigured to receive the reactant stream and produce the desiredintermediates. The condensation bed is configured to receive theintermediates for contact with the condensation catalyst and productionof the desired C4+ compounds. For systems with one or more finishingsteps, an additional reaction bed for conducting the finishing processor processes may be included after the condensation bed.

In an embodiment, the optional dehydration reaction, the optionaldehydrogenation reaction, the optional ketonization reaction, theoptional ring opening reaction, and the condensation reaction catalystbeds may be positioned within the same reactor vessel or in separatereactor vessels in fluid communication with each other. Each reactorvessel preferably includes an outlet adapted to remove the productstream from the reactor vessel. For systems with one or more finishingsteps, the finishing reaction bed or beds may be within the same reactorvessel along with the condensation bed or in a separate reactor vesselin fluid communication with the reactor vessel having the condensationbed.

In an embodiment, the reactor system also includes additional outlets toallow for the removal of portions of the reactant stream to furtheradvance or direct the reaction to the desired reaction products, and toallow for the collection and recycling of reaction byproducts for use inother portions of the system. In an embodiment, the reactor system alsoincludes additional inlets to allow for the introduction of supplementalmaterials to further advance or direct the reaction to the desiredreaction products, and to allow for the recycling of reaction byproductsfor use in other reactions.

In an embodiment, the reactor system also includes elements which allowfor the separation of the reactant stream into different componentswhich may find use in different reaction schemes or to simply promotethe desired reactions. For instance, a separator unit, such as a phaseseparator, extractor, purifier or distillation column, may be installedprior to the condensation step to remove water from the reactant streamfor purposes of advancing the condensation reaction to favor theproduction of higher hydrocarbons. In an embodiment, a separation unitis installed to remove specific intermediates to allow for theproduction of a desired product stream containing hydrocarbons within aparticular carbon number range, or for use as end products or in othersystems or processes.

The condensation reaction can produce a broad range of compounds withcarbon numbers ranging from C4 to C30 or greater. Exemplary compoundsinclude, but are not limited to, C4+ alkanes, C4+ alkenes, C5+cycloalkanes, C5+ cycloalkenes, aryls, fused aryls, C4+ alcohols, C4+ketones, and mixtures thereof. The C4+ alkanes and C4+ alkenes may rangefrom 4 to 30 carbon atoms (C4-C30 alkanes and C4-C30 alkenes) and may bebranched or straight chained alkanes or alkenes. The C4+ alkanes and C4+alkenes may also include fractions of C7-C14, C12-C24 alkanes andalkenes, respectively, with the C7-C14 fraction directed to jet fuelblend, and the C12-C24 fraction directed to a diesel fuel blend andother industrial applications. Examples of various C4+ alkanes and C4+alkenes include, without limitation, butane, butene, pentane, pentene,2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane,2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane,octene, 2,2,4,-trimethylpentane, 2,3-dimethyl hexane,2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane,decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene,tetradecane, tetradecene, pentadecane, pentadecene, hexadecane,hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene,nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene,doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane,tetraeicosene, and isomers thereof.

The C5+ cycloalkanes and C5+ cycloalkenes have from 5 to 30 carbon atomsand may be unsubstituted, mono-substituted or multi-substituted. In thecase of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C3+ alkyl, a straight chain C1+alkyl, a branched C3+ alkylene, a straight chain C1+ alkylene, astraight chain C2+ alkylene, a phenyl or a combination thereof. In oneembodiment, at least one of the substituted groups include a branchedC3-C12 alkyl, a straight chain C1-C12 alkyl, a branched C3-C12 alkylene,a straight chain C1-C12 alkylene, a straight chain C2-C12 alkylene, aphenyl or a combination thereof. In yet another embodiment, at least oneof the substituted groups includes a branched C3-C4 alkyl, a straightchain C1-C4 alkyl, a branched C3-C4 alkylene, a straight chain C1-C4alkylene, a straight chain C2-C4 alkylene, a phenyl, or any combinationthereof. Examples of desirable C5+ cycloalkanes and C5+ cycloalkenesinclude, without limitation, cyclopentane, cyclopentene, cyclohexane,cyclohexene, methyl-cyclopentane, methyl-cyclopentene,ethyl-cyclopentane, ethyl-cyclopentene, ethyl-cyclohexane,ethyl-cyclohexene, and isomers thereof.

Aryls will generally consist of an aromatic hydrocarbon in either anunsubstituted (phenyl), mono-substituted or multi-substituted form. Inthe case of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C3+ alkyl, a straight chain C1+alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenylor a combination thereof. In one embodiment, at least one of thesubstituted groups includes a branched C3-C12 alkyl, a straight chainC1-C12 alkyl, a branched C3-C12 alkylene, a straight chain C2-C12alkylene, a phenyl, or any combination thereof. In yet anotherembodiment, at least one of the substituted groups includes a branchedC3-C4 alkyl, a straight chain C1-C4 alkyl, a branched C3-C4 alkylene,straight chain C2-C4 alkylene, a phenyl, or any combination thereof.Examples of various aryls include, without limitation, benzene, toluene,xylene (dimethylbenzene), ethyl benzene, para xylene, meta xylene, orthoxylene, C9 aromatics.

Fused aryls will generally consist of bicyclic and polycyclic aromatichydrocarbons, in either an unsubstituted, mono-substituted ormulti-substituted form. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C3+ alkyl, a straight chain C1+ alkyl, a branched C3+ alkylene,a straight chain C2+ alkylene, a phenyl or a combination thereof. Inanother embodiment, at least one of the substituted groups includes abranched C3-C4 alkyl, a straight chain C1-C4 alkyl, a branched C3-C4alkylene, a straight chain C2-C4 alkylene, a phenyl, or any combinationthereof. Examples of various fused aryls include, without limitation,naphthalene, anthracene, tetrahydronaphthalene, anddecahydronaphthalene, indane, indene, and isomers thereof.

The moderate fractions, such as C7-C14, may be separated for jet fuel,while heavier fractions, (e.g., C12-C24), may be separated for dieseluse. The heaviest fractions may be used as lubricants or cracked toproduce additional gasoline and/or diesel fractions. The C4+ compoundsmay also find use as industrial chemicals, whether as an intermediate oran end product. For example, the aryls toluene, xylene, ethyl benzene,para xylene, meta xylene, ortho xylene may find use as chemicalintermediates for the production of plastics and other products.Meanwhile, the C9 aromatics and fused aryls, such as naphthalene,anthracene, tetrahydronaphthalene, and decahydronaphthalene, may finduse as solvents in industrial processes.

In an embodiment, additional processes are used to treat the fuel blendto remove certain components or further conform the fuel blend to adiesel or jet fuel standard. Suitable techniques include hydrotreatingto reduce the amount of or remove any remaining oxygen, sulfur, ornitrogen in the fuel blend. The conditions for hydrotreating ahydrocarbon stream are known to one of ordinary skill in the art.

In an embodiment, hydrogenation is carried out in place of or after thehydrotreating process to saturate at least some olefinic bonds. In someembodiments, a hydrogenation reaction may be carried out in concert withthe aldol condensation reaction by including a metal functional groupwith the aldol condensation catalyst. Such hydrogenation may beperformed to conform the fuel blend to a specific fuel standard (e.g., adiesel fuel standard or a jet fuel standard). The hydrogenation of thefuel blend stream can be carried out according to known procedures,either with the continuous or batch method. The hydrogenation reactionmay be used to remove a remaining carbonyl group or hydroxyl group. Insuch event, any one of the hydrogenation catalysts described above maybe used. Such catalysts may include any one or more of the followingmetals, Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, alloys or combinationsthereof, alone or with promoters such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi,and alloys thereof, may be used in various loadings ranging from about0.01 wt % to about 20 wt % on a support as described above. In general,the finishing step is carried out at finishing temperatures of betweenabout 80° C. to 250° C., and finishing pressures in the range of about700 kPa to 15,000 kPa. In one embodiment, the finishing step isconducted in the vapor phase or liquid phase, and uses, external H₂,recycled H₂, or combinations thereof, as necessary.

In an embodiment, isomerization is used to treat the fuel blend tointroduce a desired degree of branching or other shape selectivity to atleast some components in the fuel blend. It may be useful to remove anyimpurities before the hydrocarbons are contacted with the isomerizationcatalyst. The isomerization step comprises an optional stripping step,wherein the fuel blend from the oligomerization reaction may be purifiedby stripping with water vapor or a suitable gas such as lighthydrocarbon, nitrogen or hydrogen. The optional stripping step iscarried out in a counter-current manner in a unit upstream of theisomerization catalyst, wherein the gas and liquid are contacted witheach other, or before the actual isomerization reactor in a separatestripping unit utilizing counter-current principle.

After the optional stripping step the fuel blend can be passed to areactive isomerization unit comprising one or several catalyst bed(s).The catalyst beds of the isomerization step may operate either inco-current or counter-current manner. In the isomerization step, thepressure may vary from 2000 kPa to 15,000 kPa, preferably in the rangeof 2000 kPa to 10,000 kPa, the temperature being between 197° C. and502° C., preferably between 302° C. and 402° C. In the isomerizationstep, any isomerization catalysts known in the art may be used. Suitableisomerization catalysts can contain molecular sieve and/or a metal fromGroup VII and/or a carrier. In an embodiment, the isomerization catalystcontains SAPO-11 or SAPO41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pdor Ni and Al2O3 or SiO2. Typical isomerization catalysts are, forexample, Pt/SAPO-11/Al2O3, Pt/ZSM-22/Al2O3, Pt/ZSM-23/Al2O3 andPt/SAPO-11/SiO2.

Other factors, such as the concentration of water or undesired ointermediates, may also effect the composition and yields of the C4+compounds, as well as the activity and stability of the condensationcatalyst. In such event, the process may include a dewatering step thatremoves a portion of the water prior to the condensation reaction and/orthe optional dehydration reaction, or a separation unit for removal ofthe undesired intermediates. For instance, a separator unit, such as aphase separator, extractor, purifier or distillation column, may beinstalled prior to the condensation step so as to remove a portion ofthe water from the reactant stream containing the intermediates. Aseparation unit may also be installed to remove specific intermediatesto allow for the production of a desired product stream containinghydrocarbons within a particular carbon range, or for use as endproducts or in other systems or processes.

Thus, in one embodiment, the fuel blend produced by the processesdescribed herein is a hydrocarbon mixture that meets the requirementsfor jet fuel (e.g., conforms with ASTM D1655). In another embodiment,the product of the processes described herein is a hydrocarbon mixturethat comprises a fuel blend meeting the requirements for a diesel fuel(e.g., conforms with ASTM D975).

Yet in another embodiment of the invention, the C₂₊ olefins are producedby catalytically reacting the intermediates in the presence of adehydration catalyst at a dehydration temperature and dehydrationpressure to produce a reaction stream comprising the C₂₊ olefins. TheC₂₊ olefins comprise straight or branched hydrocarbons containing one ormore carbon-carbon double bonds. In general, the C₂₊ olefins containfrom 2 to 8 carbon atoms, and more preferably from 3 to 5 carbon atoms.In one embodiment, the olefins comprise propylene, butylene, pentylene,isomers of the foregoing, and mixtures of any two or more of theforegoing. In another embodiment, the C₂₊ olefins include C₄₊ olefinsproduced by catalytically reacting a portion of the C₂₊ olefins over anolefin isomerization catalyst. In an embodiment, a method of forming afuel blend from a biomass feedstock may comprise a digester thatreceives a biomass feedstock and a digestive solvent operating underconditions to effectively remove nitrogen and sulfur compounds from saidbiomass feedstock and discharges a treated stream comprising acarbohydrate having less than 35% of the sulfur content and less than35% of the nitrogen content based on the undigested biomass feedstock ona dry mass basis; a hydrogenolysis reactor comprising a hydrocatalytictreatment catalyst that receives the treated stream and discharges anoxygenated intermediate, wherein a first portion of the oxygenatedhydrocatalytically treated mixture is recycled to the digester as atleast a portion of the digestive solvent; a first fuels processingreactor comprising a dehydrogenation catalyst that receives a secondportion of the oxygenated hydrocatalytically treated mixture anddischarges an olefin-containing stream; and a second fuels processingreactor comprising an alkylation catalyst that receives theolefin-containing stream and discharges a liquid fuel.

The dehydration catalyst comprises a member selected from the groupconsisting of an acidic alumina, aluminum phosphate, silica-aluminaphosphate, amorphous silica-alumina, aluminosilicate, zirconia, sulfatedzirconia, tungstated zirconia, tungsten carbide, molybdenum carbide,titania, sulfated carbon, phosphated carbon, phosphated silica,phosphated alumina, acidic resin, heteropolyacid, inorganic acid, and acombination of any two or more of the foregoing. In one embodiment, thedehydration catalyst further comprises a modifier selected from thegroup consisting of Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P,B, Bi, and a combination of any two or more of the foregoing. In anotherembodiment, the dehydration catalyst further comprises an oxide of anelement, the element selected from the group consisting of Ti, Zr, V,Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn,Cd, P, and a combination of any two or more of the foregoing. In yetanother embodiment, the dehydration catalyst further comprises a metalselected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru,Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of anytwo or more of the foregoing, and a combination of any two or more ofthe foregoing.

In yet another embodiment, the dehydration catalyst comprises analuminosilicate zeolite. In one version, the dehydration catalystfurther comprises a modifier selected from the group consisting of Ga,In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and acombination of any two or more of the foregoing. In another version, thedehydration catalyst further comprises a metal selected from the groupconsisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of theforegoing, and a combination of any two or more of the foregoing.

In another embodiment, the dehydration catalyst comprises a bifunctionalpentasil ring-containing aluminosilicate zeolite. In one version, thedehydration catalyst further comprises a modifier selected from thegroup consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, alanthanide, and a combination of any two or more of the foregoing. Inanother version, the dehydration catalyst further comprises a metalselected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru,Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of anytwo or more of the foregoing, and a combination of any two or more ofthe foregoing.

The dehydration reaction is conducted at a temperature and pressurewhere the thermodynamics are favorable. In general, the reaction may beperformed in the vapor phase, liquid phase, or a combination of both. Inone embodiment, the dehydration temperature is in the range of about100° C. to 500° C., and the dehydration pressure is in the range ofabout 0 psig to 900 psig. In another embodiment, the dehydrationtemperature is in the range of about 125° C. to 450° C., and thedehydration pressure is at least 2 psig. In another version, thedehydration temperature is in the range of about 150° C. to 350° C., andthe dehydration pressure is in the range of about 100 psig to 800 psig.In yet another version, the dehydration temperature is in the range ofabout 175° C. to 325° C.

The C₆₊ paraffins are produced by catalytically reacting the C₂₊ olefinswith a stream of C₄₊ isoparaffins in the presence of an alkylationcatalyst at an alkylation temperature and alkylation pressure to producea product stream comprising C₆₊ paraffins. The C₄₊ isoparaffins includealkanes and cycloalkanes having 4 to 7 carbon atoms, such as isobutane,isopentane, naphthenes, and higher homologues having a tertiary carbonatom (e.g., 2-methylbutane and 2,4-dimethylpentane), isomers of theforegoing, and mixtures of any two or more of the foregoing. In oneembodiment, the stream of C₄₊ isoparaffins comprises of internallygenerated C₄₊ isoparaffins, external C₄₊ isoparaffins, recycled C₄₊isoparaffins, or combinations of any two or more of the foregoing.

The C₆₊ paraffins will generally be branched paraffins, but may alsoinclude normal paraffins. In one version, the C₆₊ paraffins comprises amember selected from the group consisting of a branched C₆₋₁₀ alkane, abranched C₆ alkane, a branched C₇ alkane, a branched C₈ alkane, abranched C₉ alkane, a branched C₁₀ alkane, or a mixture of any two ormore of the foregoing. In one version, the C.sub.6+ paraffins comprisedimethylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, methylpentane,2-methylpentane, 3-methylpentane, dimethylpentane, 2,3-dimethylpentane,2,4-dimethylpentane, methylhexane, 2,3-dimethylhexane,2,3,4-trimethylpentane, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane,2,3,3-trimethylpentane, dimethylhexane, or mixtures of any two or moreof the foregoing.

The alkylation catalyst comprises a member selected from the group ofsulfuric acid, hydrofluoric acid, aluminum chloride, boron trifluoride,solid phosphoric acid, chlorided alumina, acidic alumina, aluminumphosphate, silica-alumina phosphate, amorphous silica-alumina,aluminosilicate, aluminosilicate zeolite, zirconia, sulfated zirconia,tungstated zirconia, tungsten carbide, molybdenum carbide, titania,sulfated carbon, phosphated carbon, phosphated silica, phosphatedalumina, acidic resin, heteropolyacid, inorganic acid, and a combinationof any two or more of the foregoing. The alkylation catalyst may alsoinclude a mixture of a mineral acid with a Friedel-Crafts metal halide,such as aluminum bromide, and other proton donors.

In one embodiment, the alkylation catalyst comprises an aluminosilicatezeolite. In one version, the alkylation catalyst further comprises amodifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag,Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or moreof the foregoing. In another version, the alkylation catalyst furthercomprises a metal selected from the group consisting of Cu, Ag, Au, Pt,Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os,an alloy of any two or more of the foregoing, and a combination of anytwo or more of the foregoing.

In another embodiment, the alkylation catalyst comprises a bifunctionalpentasil ring-containing aluminosilicate zeolite. In one version, thealkylation catalyst further comprises a modifier selected from the groupconsisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, alanthanide, and a combination of any two or more of the foregoing. Inanother version, the alkylation catalyst further comprises a metalselected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru,Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of anytwo or more of the foregoing, and a combination of any two or more ofthe foregoing. In one version, the dehydration catalyst and thealkylation catalyst are atomically identical.

The alkylation reaction is conducted at a temperature where thethermodynamics are favorable. In general, the alkylation temperature isin the range of about −20° C. to 300° C., and the alkylation pressure isin the range of about 0 psig to 1200 psig. In one version, thealkylation temperature is in the range of about 100° C. to 300° C. Inanother version, the alkylation temperature is in the range of about 0°C. to 100° C., and the alkylation pressure is at least 100 psig. In yetanother version, the alkylation temperature is in the range of about 0°C. to 50° C. and the alkylation pressure is less than 300 psig. In stillyet another version, the alkylation temperature is in the range of about70° C. to 250° C., and the alkylation pressure is in the range of about100 psig to 1200 psig. In one embodiment, the alkylation catalystcomprises a mineral acid or a strong acid and the alkylation temperatureis less than ° C. In another embodiment, the alkylation catalystcomprises a zeolite and the alkylation temperature is greater than 100°C.

Without wishing to be limited by theory, it is believed that the organicphase solvent is effective in preventing tar or heavy ends depositionduring biomass digestion, and in assisting with the digestion viasolvation. It is also known that hydrogen solubility is greater inorganic solvents vs. water, such that for a given system pressure ofhydrogen, hydrogenation reactions are accelerated by the improvedsolubility afforded by use of organic, hydrocarbon-rich solvent.

To facilitate a better understanding of the present invention, thefollowing examples of certain aspects of some embodiments are given. Inno way should the following examples be read to limit, or define, theentire scope of the invention.

EXAMPLES

Reaction studies for Examples 1-12 were conducted in a Parr5000Hastelloy multireactor comprising 6×75-milliliter reactors operated inparallel at pressures up to 135 bar, and temperatures up to 275° C.,stirred by magnetic stir bar. Reaction samples were analyzed for sugar,polyol, and organic acids using an HPLC method entailing a Bio-RadAminex HPX-87H column (300 mm×7.8 mm) operated at 0.6 ml/minute of amobile phase of 5 mM Sulfuric Acid in water, at an oven temperature of30° C., a run time of 70 minutes, and both RI and UV (320 nm) detectors.

Product formation (mono-oxygenates, glycols, diols, alkanes, acids) weremonitored via a gas chromatographic (GC) method “DB5-ox”, entailinga60-m×0.32 mm ID DB-5 column of 1 μm thickness, with 50:1 split ratio, 2ml/min helium flow, and column oven at 40° C. for 8 minutes, followed byramp to 285° C. at 10° C./min, and a hold time of 53.5 minutes. Injectortemperature is set at 250° C., and detector temperature at 300° C.

Gasoline production potential by condensation was assessed via injectionof one microliters of liquid intermediate product into a catalytic pulsemicroreactor entailing a GC insert packed with 0.12 grams of ZSM-5catalyst, held at 375° C., followed by Restek Rtx-1701 (60-m) and DB-5(60-m) capillary GC columns in series (120-m total length, 0.32 mm ID,0.25 um film thickness) for an Agilent/HP 6890 GC equipped with flameionization detector. Helium flow was 2.0 ml/min (constant flow mode),with a 10:1 split ratio. Oven temperature was held at 35° C. for 10minutes, followed by a ramp to 270° C. at 3° C./min, followed by a 1.67minute hold time. Detector temperature was 300° C.

Example 1 Aqueous Phase Hydrolysis and Reduction of Biomass

2.002 grams of ground soft pine wood (16% moisture; 67.8% carbohydrateon dry basis) were charged with 20.44 grams of deionized water, and0.451 grams of 5% Ru/C Escat 4401 catalyst (from Strem Chemicals, Inc.,50% wet), to a Parr 5000 reactor. The reactor was pressured to 54 barwith H₂, and ramped from 170-240° C. over 6 hours, before maintaining240° C. overnight to complete reaction. Following reaction, solids wererecovered by filtration on Whatman #2 filter paper, and oven driedovernight at 90° C. to assess the extent of digestion of biomoass.Results indicated greater than 90% digestion of the softwood charged,into liquid soluble products.

Gas chromatographic analysis of a sample of the resulting aqueous phaseusing the DB5-ox method indicated the presence of 1.41 wt % productsrelative to n-butanol internal standard. This corresponded to 41% of thetheoretical yield, basis the carbohydrate content of the wood charged.

Example 2 Organic Phase Hydrolysis and Reduction of Biomass

2.007 grams of ground soft pine (16% moisture) were charged with 20.21grams of a solvent comprising 8% deionized water and 92% 1-pentanol, and0.455 grams of 5% Ru/C Escat 4401 catalyst (from Strem Chemicals, Inc.,50% wet), to a Parr 5000 reactor. This solvent composition was in thesingle phase region at 298 K, but near the phase boundry for maximumwater solubility in 1-pentanol of 9. 8-10.2 wt %, as reported by M.Góral, B. Wiśniewska-Goclowska, and A. M

czyńskia in Recommended Liquid-Liquid Equilibrium Data, Part 4:1-Alkanol—Water Systems, J. Phys. Chem. Ref. Data, Vol. 35, No. 3, 2006.Water solubility is increased at reaction temperature.

The reactor was pressured with hydrogen to 54 bar, and heated using thesame schedule as Example 1. Filtration again revealed greater than 90%digestion of wood. Gas chromatographic analysis of the solvent phase viathe DB5-ox method indicated 107% of the theoretical yield of hydrocarbonand oxygenate components of retention less than sorbitol (hexosealcohol), basis the carbohydrate content of the wood charged. Excessyield above theoretical carbohydrate conversion may be due toexperimental error, or to conversion of a portion of the lignin fractionto targeted intermediates.

This result show the superior ability of the 1-pentanol-rich solvent insolubilizing the reaction products of biomass hydrolysis, relative towater only as solvent in example 1.

Examples 3-6

The experiment of example 1 was repeated with 1-pentanol (examples 3 and4), 1-octanol (example 5), and toluene (example 6) as solvent, andvarying amounts of water relative to solubility limits in alcoholsolvents reported by R. Stephenson, J. Stuart, M. Tabak, J. Chem. Eng.Data 1984, 29, 287-290, and in toluene as reported by B. J. Neely, J.Wagner, R. L. Robinson, Jr., K. A. M. Gasem, J. Chem. Eng. Data 2008,53, 165-174. Reaction conditions and conversions are shown in Table 1.Examples #3, 4, and 6 used 5% Ru/C Escat 4401 catalyst (from StremChemicals, Inc., 50% wet) as catalyst. Example #5 used DC-2534 sulfidedcobalt molybdate hydrotreating catalyst from Criterion Catalyst &Technologies L.P., and entailed addition of alanine and cysteine to thesolvent mixture to model amino acids present in recycle solventgenerated in a continuous process.

TABLE 1 Parr5000 Wood Digestion and Reaction H₂O wt % Dry GC yield H₂Osolubility Amino wt % wood % (% Ex Solvent wt % 20-25° C. acid Catalystcatalyst digest theoretical) 3 1-pentanol 9.30 10.21 none 5% Ru/C 1.1474.0 115.1 4 1-pentanol 9.30 10.21 ala + cys* DC2534S 1.74 90.7 117.2 51-octanol 3.30 4.90 none 5% Ru/C 1.13 79.2 166.7 6 toluene 1.30 0.03none 5% Ru/C 1.15 71.9 21.6 170-240° C. ramp (6-h) followed by overnight240° C.; 54 bar H₂ charged at room temperature. *Ex#4 with 1500 ppmalanine, 150 ppm cysteine. Cat

The examples demonstrated greater than 70% digestion of wood biomass.Observed GC yields of intermediates of retention time less than C₆ sugaralcohol were greater than 100%, which may be attributable to digestionor solubilization of lignin also present in the wood feed. GC yieldswere lowest for toluene as solvent, where no water was added beyond thatpresent in the ground wood charged to the reactor. This result suggeststhat water may be needed at higher concentrations to effect hydrolysisof the woody biomass, to produce components which can elute from the GCanalysis.

Examples 7-11

The experiments of examples 3-6 were repeated, with multiple additionsof pine wood to obtain a high actives concentration in the reactionsolution, calculated from filtration results as the percent digestion ofwood, relative to solvent present. Results demonstrate that for allsolvent systems, more than 55% digestion of woody biomass could bedigested over three cycles, to obtain an actives concentration insolution of greater than 10 weight percent. Observable intermediates viaGC analysis was greater than 70% of the expected yields, except for therun with toluene where a lower concentration of water was used. Totalwater concentrations approached or exceeded the solubility limit forwater in solvent at room temperature. Water solubilities increase withtemperature, as reported by Stephenson et al. and Neely et al. (op.cit), however, such that all systems were undersaturated with waterunder reaction conditions.

TABLE 2 Multicycle additions of wood biomass, 170-240° C. digestion, 52bar H₂ H₂O wt % GC yield H₂O solubility Amino wt % wood % (% % Solventwt % 20-25 C. acid Catalyst cat digest theory) active 1-pentanol 10.0510.21 none 5% Ru/C 1.13 60.8 76.8 10.9 1-pentanol 10.05 10.21 ala + cys*DC2534S 1.80 57.3 69.8 10.4 1-octanol 5.44 4.90 none 5% Ru/C 1.15 72.096.7 12.6 toluene 1.30 0.03 none 5% Ru/C 1.13 60.6 22.2 10.9

Final reaction samples were injected onto the ZSM-5 catalytic pulsemicroreactor, and revealed the formation of alkanes, as well as benzene,toluene, ethylbenzene, tri-methyl benzenes, xylenes, and naphthalenes.

Example 12 In Situ Formation of Organic Rich Solvent Phase

A microflow reactor was packed with 4.53 grams of Criterion DC2534catalyst, and tested via feed of C₆ sugar alcohol (sorbitol) asrepresentative of the hydrolysis of cellulosic biomass. A feed of 48 wt% sorbitol in deionized water was passed through the catalyst bed at aweight hourly space velocity of 0.3/hour, along with H₂ feed at anexcess flow of 9.5 ml/min (measured at 25 C and atmospheric pressure),with bed temperature varied from 240-260° C. Liquid product comprised anupper hydrocarbon-rich (“oil”) layer, and an aqueous layer, with theoil-rich layer comprising 7-15 volume percent of the total liquidproducts. On day 20 for example, the oil-rich layer comprised 15% of thevolume of liquid product obtained following operation at 260° C., whileon day 24 the oil fraction was reduced to 10% of total product, uponoperation at 250° C. Analysis via liquid chromatography indicated morethan 80% conversion of sorbitol to hydrogenated products.

Analysis of liquid product via a combined Gas-chromatography-MassSpectrometry (GCMS) method indicated the formation of ketones andalcohols greater or equal to than C4 (1-butanol), and especiallypentanols and hexanols, which comprise the hydrocarbon-rich phase (“oil”layer) formed. This example shows the in situ formation ofnon-water-miscible, hydrocarbon-rich solvent via hydrogenation of sugaralcohols.

TABLE 3 GC MS of upper hydrocarbon rich phase from hydrogenation of 48%sorbitol solution Comp # Compound Name RT (min) Area % 1 Water 7.9463.9% 2 Methanol 8.426 2.3% 3 Ethanol 9.456 0.9% 4 2-Propanol 10.515 3.8%5 1-Propanol 12.775 4.6% 6 2-Butanone 14.375 1.7% 7 2-butanol 15.0515.4% 8 Furan, 2-methyl 15.487 1.4% 9 Hexane 15.918 7.6% 10 3-Hexene16.035 0.6% 11 2-Hexene 16.233 1.7% 12 1-Butanol 20.147 1.4% 132-Pentanone 21.929 2.4% 14 3-Pentanone 22.999 2.1% 15 2-Pentanol 23.8335.1% 16 3-Pentanol 23.912 4.2% 17 Furan, 2-ethyl- 24.425 4.4% 18 Furan,2,5-dimethyl- 25.088 6.8% 19 1-Pentanol 31.559 1.0% 20 3-Hexanone 32.8553.8% 21 2-Hexanone 33.134 3.6% 22 3-Hexanol 34.238 5.3% 23 2-Hexanol34.585 12.0% 24 Cyclopentanone, 2- 36.662 0.5% methyl- 25 1-Pentanol,2-methyl 37.014 0.8% 26 Cyclopentanol, methyl 37.342 1.3% 27Cyclopentanol, methyl 37.479 0.8% 28 1-Hexanol 39.044 7.4% 29 Unknown39.691 1.2% 30 3-Heptanone 39.786 1.0% 31 3-Heptanol 40.509 0.7% 324-Octanone 43.606 0.2%

Example 13

A 75-ml Parr 5000 reactor was fitted with glass liner and charged with15.04 grams of 1-octanol solvent, and 0.118 grams of potassium carbonatebuffer. 503 grams of nickel-oxide promoted cobalt molybdate catalystwere then added (DC-2534, containing 1-10% cobalt oxide and molybdenumtrioxide (up to 30 wt %) on alumina, and less than 2% nickel, obtainedfrom Criterion Catalyst & Technologies L.P.), and sulfided by the methoddescribed in US2010/0236988 Example 5.

The reactor was charged with 2.7 grams of southern pine mini-chips (39%moisture), of nominal size 3×5×5 mm in dimension before pressuring with52 bar of hydrogen under stirring via stir bar. The reactor was heatedto 190° C. for 1 hour before ramping over 15 minutes to a temperature of250° C. and holding, to complete a 5-hour cycle.

The process was repeated for 6 cycles of wood addition, with addition ofpotassium carbonate as needed to maintain pH between 6-7. Virtually allwood was digested across 6 cycles. The oil and aqueous layers wereanalyzed by gas chromatography using a 60-m×0.32 mm ID DB-5 column of 1μm thickness, with 50:1 split ratio, 2 ml/min helium flow, and columnoven at 40° C. for 8 minutes, followed by ramp to 285° C. at 10° C./min,and a hold time of 53.5 minutes. The injector temperature was set at250° C., and the detector temperature was set at 300° C.

A range of alkanes, ketone and aldehyde monooxygenates as well as glycolsolvents and products, and polyols (glycerol) were observed, withvolatility greater than C6 sugar alcohol sorbitol. GC measured productsindicated a yield of 90% of products with volatility greater thansorbitol (C6 monomer), relative to the dry weight of wood initiallycharged.

What is claimed is:
 1. A method comprising: (a) providing a biomassfeedstock containing cellulose and water; (b) contacting the biomassfeedstock with an organic solvent having partial miscibility with waterat 25° C. to form a digested biomass stream containing the organicsolvent and water at an organic solvent to water mass ratio of greaterthan 1:1; (c) contacting the digested biomass stream with molecularhydrogen in the presence of a metal catalyst capable of activatingmolecular hydrogen, under organic phase hydrothermal conditions to forma hydrocatalytically treated mixture that contains a plurality ofhydrocarbon molecules and oxygenated hydrocarbon molecules; (d) phaseseparating the hydrocatalytically treated mixture, by liquid-liquidseparation, into an organic hydrocarbon-rich phase and a water phasecomprising water soluble oxygenated hydrocarbons; (e) providing at leasta portion of the organic hydrocarbon-rich phase to step (b) to form atleast a portion of the organic solvent; and (f) processing at least aportion of the water phase, at least a portion of the organichydrocarbon-rich phase, or at least a portion of both water phase andorganic hydrocarbon-rich phase, to form a fuel blend comprising higherhydrocarbons.
 2. The method of claim 1 wherein water is present in theorganic phase at a concentration of less than 50 weight percent.
 3. Themethod of claim 2 wherein water is present in the organic phase at aconcentration of less than 15 weight percent.
 4. The method of claim 1wherein the fuel blend comprises at least one composition selected fromthe group consisting of: a fuel additive, a gasoline fuel, a dieselfuel, and a jet fuel.
 5. The method of claim 1 wherein step (f)comprises processing in the presence of a hydrogenation catalyst to formthe fuel blend.
 6. The method of claim 1 wherein step (c) is carried ata temperature in the range of 60° C. to 300° C.
 7. The method of claim 1wherein step (f) comprises processing in the presence of a condensationcatalyst to form the fuel blend, wherein the fuel blend comprises agasoline fuel.
 8. The method of claim 1 wherein step (f) comprisesprocessing in the presence of an acid catalyst to form at least someolefins; and contacting the olefins with an oligmerization catalyst toform the fuel blend.
 9. The method of claim 1 wherein thehydrocatalytically treated mixture has a total organic content on aweight basis of greater than 50%.
 10. The method of claim 1 wherein themetal catalyst capable of activating molecular hydrogen is a catalysthaving a support material that has incorporated therein or is loadedwith a metal component, which is or can be converted to a metal compoundthat has activity towards the catalytic hydrogenation, hydrogenolysis,and hydrodeoxygenation of soluble carbohydrates.
 11. The method of claim1 wherein step (b) is carried out at a temperature in the range from100° C. to 300° C.
 12. The method of claim 11 wherein step (b) iscarried out at a pressure in a range from about 7 to 200 bar.
 13. Themethod of claim 1 wherein the organic hydrocarbon-rich phase has adielectric constant of greater than about
 2. 14. The method of claim 11wherein step (c) is carried out at a temperature in the range of 110° C.to 300° C.,